Chromium compound of azo dyestuffs and a process of making same.



sienna GAIHENT ENGI AND GARL JAGEBSPAJHEE, E BASEL, SWITZERLAND, ASSIGNORS TO SQC'LETY 0F CHEMICAL INDUSTRY IN BASLE, OF BASEL,- SWITZERLAND.

GHEUMIUIE CGDJIPOUNID 0F AZO DYESTUFFS AND PRGCESS OF MAKING SAME.

Specification of Letters Patent.

Patented ot. 9, 1917.

Ho Drawing. Original application filed November 29, 1815, Serial No. 64,023. Divided and. this application filed August 3, i916. Serial No. 112,950.

T 0 all "whom may concern:

Be it known that we, Dr. GADIENT ENGI and Dr. CARL Juonusrnormu, both chemists, citizens of the Swiss Republic, and residents of Basel, Switzerland, have invented new Chromium Compounds of Azo Dyestufi's and Processes of Making Same, of which the following is a full, clear, and exact specification.

This application is a divisional one of our application for Letters Patent Ser. No.

64,023, filed November 29, 1915.

We have found that the new chromium compounds of azodyestulis containing at least one group able to combine with chromium which can he obtained, according to our application for Letters Patent Ser. No. 64023, filed November 29, 1915, by combining the hitherto unknown. chromium compound of an orthooxydiazobody with an M10- dyestufi component containing at least one group able to he chromated, can. be converted into chromium compounds wherein all of the groups able combine with chromiiun are saturated with chromium, by

treating a hot aqueous solution or SllSlfitbIlSlOIl.

of the said half chromated dyestuffs with chromium compound as for instance ohro mi'um oXid or a chromium salt. The. thus 3 obtained saturated chromium compounds of orthooxyazodyestufis constitute intense colored powders dissolving in water to intense.

colored solutions which do not undergo any essential change by adding sodium carbonate or sodalye. They dye animal fiber in an acid hath fast tints which are not changed when subsequently chromated.

The process for the manufacture of these compounds is illustrated by the following examples: I I

Example 1: 15.4 parts 4:2:1-nitr0amind phenol are heated with 350 parts water, 18% parts crystallized sodium acetate and parts chromium fiuorid for 3 to 4 hours at i06 C. in a vessel provided Witha reflux cooler. After the mass is completely cooled :fiown, the residue is separated by filtration.

and the filtered liquid saturated with comluon salt. The easily soluble chromium c0msound of at z 2: l-nitroaminophenol separates v *ogressiyely as a yellow-brown precipitate.

.rug' diazooody is cemhinedw th otized in known mamler and l:8:3:6-amiuonaphtholdisulfonic acid in a chroinated dyestuff is precipitated from the filtered liquid by adding common salt. The dyestuff' can, if desired, be purified by redissolution. 2.5 parts of this half chr0- mated dye'stufl are added to a, solution of 2.5 parts chromium fiuorid in parts boiling water. The violet solution turns quickly to blue-Violet and after a certain boiling to blue-green. After a boiling for a of an hour, 6 parts crystallized sodium acetate are added, and the liquid is separated hot by filtration and suction from the undissolved residue, evaporated. to about 25 parts and the chromium compound is precipitated from it by adding- 6 parts common salt. After the mass has been allowed to stand for a long time, the chromium compound is separated by filtration and'suction, slightly washed and-dried. It dyes wool and other animal fiber in an acid bath pure green tints very fast to alkalis, light, Washing,

pound is very easily soluble, its solution is concentrated diazotized in the known man nor and combined with a soda alkaline soluoi"? sodium-betanaphtholate. The solu tion of dyestufi' is heated in order to dis solve the partly separated dyestufi? and filtered; from the filtered liquid the dyestuil is precipitated by addition of common salt and eventually purified by redissolution.

5 parts of this half chromated dyestufi' are ldissol ed in parts hot water, and to the thus obtained solution 12 -parts sodium aceadded, whereby theblue-red solution becomes more yellow. Hereafter the mass is tate and" 2.5 parts chromium fluorid' are Y I so dill

of common salt.

red coloration.

\ Example 3: 19.9 parts picranric acid are boiled with 1750 parts water, 10.5 parts chromium fiuorid and 13.6 parts crystallized sodium acetate, for about 15 hours, in

a vessel provided with a reflux cooler and then. filtered hot. There remains a residue 1. The filtered liquid is concentrated by evaporatiomwhereby a precipitate ll separates, which is isolated by filtration and suction. Both parts I and H of the new chromium compound are diazotized in known manner and united with a sodaalkaline solu tion of 1:8:2: -aminonaphtholdisulfonic acid. in both cases the difiicultly soluble dyestufi precipitated and is separatedby filtration from the mother-lye free of dyestufi. The dye'stufi is then extracted with water, the thus obtained solution is filtered and from the filtered liquid the dyestufi' is iso-. lated by adding common salt 3 parts of this half chromated dyestud are dissolved in 60 parts hot water and to the thus obtained violet-blue solution are added 1.5 parts chromium fluorid and 3 parts sodium acetate. The whole is heated for a short time, whereby the coloration of the reaction mass turns to blue-green. After a boiling of 1 hour, the hot liquid is separated from the residue by filtration and suction, evaporated to the halfiof its volume and salted out. The obtained entirely chromated dyestufl dyes wool in acid bath yellowislrgreen tints of excellent fastness. It dissolves in concentrated sulfuric acid with violet-red coloration, in water and in alcohol with green colorations.

. Instead of the chromium fluorid specified in the examples other salts of chromium as chromium chlorid, chromium sulfate, etc., can be employed.

The chromium compounds able to be prepared according to the described process can be employed for instance for producing fast tints on the animal fibers according to the process of U. S. plication for Letters Patent Ser; No. 6382?, filed November'Q'Z, 1915.

at we claim is:

1. The described process for the manufacture of chromium compounds of orthooxyazodyestufls consisting in treating an orthoaminophenol compound with a chromium compound in a hot aqueous medium, diazotizing the thus obtained chromium. compound use lanes of orthoaminophenol compound, combining the resulting chromium coinptumd of ortho oxydiazobody with an azodyestuil" component containing at least one group able to be chromated, and'treating'finally the thus obtained half chromated orthooxy azodyestufl' in a hot aqueous medium with'a chromium compound.

2. The described process for the manufac ture of chromium compounds of orthooxy- 'azodyestufi's consisting in treating an orthoaminophcnol compound with a chromium compound. in a hot aqueous medium, diazo tiziug the thus obta ned chromium compound of orthoaminophenol compound, combining the resulting chromium compound of orthooxydiazobody with naphtholic com pound and treating finally the thus obtained half chromated orthooxyazodyestufi in a hot aqueous medium with a chromium compound.

3. The described process for the manufacture of chromium compounds of orthooxyazodyestulis consisting in treatin an orthoaminophenol compound with a chromium compound in a hot aqueous medium, diazo tizing the thus obtained chromium-compound of orthoaminophenol compound, combining the resulting chromium compound of orthooxydiazobody with an aminonaphtholsulfomc compound and treating finally the thus obtained half chromated, orthooxyazodyestuif in a hot aqueous medium with a chro mium compound. l

4:. As new products, the described chromium compounds of orthooxyazodyestufis, in which all groups able to combine with chromium are saturated with chromium, dyeing animal fibers in acid baths fast dyeings which are not changed when subsequently chromated, and constituting intense colored powders dissolving in water to intense colored solutions which do not undcrgo any essential change by adding sodium carbona-zo or lye 5. As .u products, the described chromium compounds of orthooxyazodyestufi's derived from an orthodiazophenol compound and a naphtholic compound and in which all groups able to combine with chromium are saturated with chromium, dyeing animal fibers in acid bath fast dyeings which are not changed, when subsequently chromated and constituting intense colored powders dissolving in water to intense colored solutions which do not undergo any essential change by adding sodium carbonate or soda lye.

6. As new products the described chromium compounds of orthooxyazodyestufls derived from an orthodiazophenol compound and an aminonaphtholsulfonic compound and in which all groups able to com- I bine with chromium are saturated with chromium, dyeing animal fibers in acid baths fast 1,eee,eee

dyeings whih are not changed when subsesigned our names this 12th day of July quently chromated and'constituting intense 1916, in the presemxe of e subscribing witcolored powders dissolving in .Water to inness. 1' I tense colored solutions which do not un- DR. GADIENTENGI. 5 dergo any essential change by edding'sodium DR. CARL JAGERSPAOHER.

' carbonate or soda lye. Witness:

In Witness whereof we have hereunto 'AMAND R 

